Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/52—Phosphorus bound to oxygen only
  • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
  • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
  • C08K5/5333—Esters of phosphonic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

Definitions

• thermoplastic polymer mixtures which contain special, halogen-free polycarbonates composed of 50 mol% to 100 mol% of tetraalkylated bisphenol carbonate structural units, halogen-free styrene polymers and / or halogen-free graft polymers, halogen-free Contain phosphate esters and optionally tetrafluoroethylene polymers.
• V-O values are 1.6 mm only in the presence of component D) and / or when using halogenated polycarbonate as component A) according to UL-94.
• DE-OS 3 521 388 discloses thermoplastic molding compositions with flame-retardant properties, the halogen-free polycarbonates, copolymers of styrenes with maleic anhydride, phosph (on) atester, tetrafluoroethylene polymers and 0.1 to 3 parts by weight of graft polymers included, the graft polymers in turn having been co-precipitated with the tetrafluoroethylene polymers.
• these molding compounds have V - O at 1.6 mm, the toughness, flow seam strength and stress crack resistance are not yet sufficient for numerous applications.
• DE-OS 3 523 314 (Le A 23 940) discloses impact-resistant, flame-retardant molding compositions which contain halogen-free polycarbonates, halogen-free styrene-acrylonitrile copolymers, phosphorus compounds, tetrafluoroethylene polymers and 0.1 to 3 parts by weight of graft polymers, where the graft polymers in turn have been co-precipitated with the tetrafluoroethylene polymers.
• the toughness, flow seam strength and stress crack resistance of the molding compositions according to DE-OS 3 523 314 is, however, not yet sufficient for some applications, in particular in the case of complicated, flame-retardant moldings such as housing parts, where design-related openings, webs and the like. ⁇ . require the highest possible level of the above properties.
• Molding compositions of this type have the disadvantage of a narrower processing range and flow seam strength compared to the molding compositions according to the invention.
• the technical advantage of the molding compositions according to the invention lies in the extremely advantageous combination of toughness, resistance to stress cracking and flame resistance, the latter being achieved without halogen (Br, Cl) and metal compounds.
• Thermoplastic, halogen-free, aromatic polycarbonates according to component A) which are suitable according to the invention are those based on the diphenols of the formula II, wherein A is a single bond, C1-C5-alkylene, C2-C5-alkylidene, C5-C6-cycloalkylidene, -S- or -SO2-.
• Suitable diphenols of the formula (II) are, for example, hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane or 1,1-bis (4-hydroxyphenyl) cyclohexane.
• Preferred diphenols of the formula (II) are 2,2-bis (4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) cyclohexane.
• the diphenols of the formula (II) are either known from the literature or can be prepared by processes known from the literature.
• the preparation of the polycarbonates according to component A) which are suitable according to the invention is known from the literature and can be carried out, for example, with phosgene according to the phase interface process or with phosgene according to the process in homogeneous phase (the so-called pyridine process), the molecular weight to be set in each case being known in a known manner by a corresponding amount of known Chain breakers is achieved.
• Suitable chain terminators are, for example, monophenols such as phenol itself, p-cresol, p-tert-butylphenol and p-isooctylphenol.
• the polycarbonates according to component A) which are suitable according to the invention have average weight molecular weights ( M w , measured for example by ultracentrifugation or by scattered light measurement) from 10,000 to 200,000, preferably from 20,000 to 80,000.
• polycarbonates according to component A) which are suitable according to the invention are both homopolycarbonates and copolycarbonates.
• polycarbonates according to component A) which are suitable according to the invention can be branched in a known manner, preferably by incorporating 0.05 to 2.0 mol%, based on the sum of the diphenols used, of three- or more than three-functional compounds, for example those with three or more than three phenolic OH groups.
• Halogen-free polycarbonates in the sense of the present invention means that the polycarbonates are composed of halogen-free diphenols, halogen-free chain terminators and optionally halogen-free branching agents, the content of minor ppm amounts of saponifiable chlorine resulting, for example, from the preparation of the polycarbonates with phosgene according to the Phase boundary process, is not to be regarded as containing halogen in the sense of the invention.
• Such polycarbonates with ppm contents of saponifiable chlorine are halogen-free polycarbonates in the sense of the present invention.
• Rubbers suitable for producing the halogen-free graft polymers B) are in particular polybutadiene, butadiene / styrene copolymers (both also copolymerized with up to 30% by weight, based on the weight of rubber, of a lower alkyl ester of acrylic or methacrylic acid such as methyl methacrylate, ethyl acrylate, methyl acrylate or ethyl methacrylate), polyisoprene, alkyl acrylate rubbers (from C1-C8 alkyl acrylates, especially ethyl, butyl, ethylhexyl acrylate) .
• the alkyl acrylate rubbers can optionally contain up to 30% by weight, based on rubber weight, of monomers such as vinyl acetate, acrylonitrile, styrene, methyl methacrylate and / or vinyl ether in copolymerized form, and smaller amounts, preferably up to 5% by weight, based on rubber weight, have a crosslinking effect , ethylenically unsaturated monomer.
• Such crosslinkers are e.g. B.
• alkylenediol di (meth) acrylates polyester di (meth) acrylates, divinylbenzene, trivinylbenzene, triallyl cyanurate, allyl (meth) acrylate, butadiene or isoprene.
• acrylate rubbers are those which contain a crosslinked diene rubber from one or more conjugated dienes and optionally an ethylenically unsaturated monomer, such as styrene and / or acrylonitrile, as the core.
• Other suitable rubbers are, for example, EPDM rubbers, ie rubbers made of ethylene, propylene and an unconjugated diene, and silicone rubbers.
• Preferred rubbers for the preparation of the graft polymers B) are diene and alkyl acrylate rubbers.
• the rubbers are in the graft polymers B) in the form of at least partially crosslinked particles having an average particle size of 0.09 to 5 ⁇ m, in particular 0.1 up to 1 ⁇ m.
• the graft polymers B) are prepared by radical graft copolymerization of the monomer mixtures defined at the outset from B.1.1) and B.1.2) in the presence of the rubbers B.2) to be grafted and are known throughout.
• Preferred production processes for the graft polymers B) are emulsion, solution, bulk or suspension polymerization.
• Particularly preferred graft polymers B) are the so-called ABS polymers.
• nucleus-substituted styrenes are nucleus alkylated styrenes such as. e.g. B. p-methylstyrene to understand.
• Copolymers according to component C) often arise as by-products in the graft polymerization to produce component B), especially when large amounts of monomers are grafted onto small amounts of rubber.
• the amount of copolymer C) to be used according to the invention does not include these by-products of the graft polymerization.
• copolymers according to component C) are resin-like, thermoplastic and rubber-free.
• Particularly preferred copolymers C) are those made from styrene with acrylonitrile and optionally with methyl methacrylate, from ⁇ -methylstyrene with acrylonitrile and optionally with methyl methacrylate, or from styrene and ⁇ -methylstyrene with acrylonitrile and optionally with methyl methacrylate.
• thermoplastic copolymer C is 60 to 80% by weight of C.1) and 40 to 20% by weight of C.2).
• the styrene-acrylonitrile copolymers according to component C) are known and can be prepared by radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization.
• the copolymers according to component C) preferably have molecular weights M w (weight average, determined by light scattering or sedimentation) between 15,000 and 200,000.
• halogen-free phosphorus compounds according to component D) which are suitable according to the invention are generally known (see, for example, Ullmann, Encyclopedia of Industrial Chemistry, Vol. 18, pp. 301 ff, 1979; Houben-Weyl, Methods of Organic Chemistry, Vol. 12/1, p 43; Beilstein, Vol. 6, p. 177).
• Phosphorus compounds according to component D), formula (I), which are suitable according to the invention are, for example, triphenyl phosphate, tricresyl phosphate, diphenyl-2-ethylcresyl phosphate, tri- (iso-propylphenyl) phosphate, methylphosphonic acid diphenyl ester, phenylphosphonic acid diethyl ester, diphenylcresyl phosphate and tribhenyl phosphate.
• the tetrafluoroethylene polymers according to component E) which are suitable according to the invention are polymers with fluorine contents of 65 to 76% by weight, preferably 70 to 76% by weight.
• Examples are polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymers or tetrafluoroethylene copolymers with small amounts of fluorine-free, copolymerizable, ethylenically unsaturated monomers.
• the polymers are known.
• ком ⁇ онентs can be prepared by known processes, for example by polymerizing tetrafluoroethylene in an aqueous medium with a free radical-forming catalyst, for example sodium, potassium or ammonium peroxydisulfate at pressures from 7 to 71 kg / cm2 and at temperatures from 0 to 200 ° C., preferably at temperatures from 20 to 100 ° C. (For more details see, for example, US Pat. No. 2,393,967.) Depending on the form of use, the density of these materials can be between 1.2 and 2.3 g / cm 3, the average particle size between 0.05 and 1,000 ⁇ m.
• a free radical-forming catalyst for example sodium, potassium or ammonium peroxydisulfate
• Polytetrafluorethylenes preferred according to the invention have average particle sizes of 0.05 to 20 ⁇ m, preferably 0.08 to 10 ⁇ m, and a density of 1.2 to 1.9 g / cm3 and are in the form of a coagulated mixture of emulsions of the tetrafluoroethylene polymers E) Emulsions of the graft polymers B) are used.
• Suitable tetrafluoroethylene polymers E) which can be used in powder form have, for example, particle sizes of 100 to 1,000 ⁇ m and densities of 2.0 g / cm3 to 2.3 g / cm3.
• tetrafluoroethylene polymers in particular reduces or completely prevents the mold melt from dripping off during the firing process; the use in the form of a coagulated mixture also improves the surface of moldings produced from the mixtures according to the invention, which is particularly important for the production of very large parts or for the production at very high processing temperatures.
• Suitable tetrafluoroethylene polymer emulsions usually have solids contents of 30 to 70% by weight, in particular 50 to 60% by weight.
• the emulsions of the graft polymers B) have solids contents of 25 to 50% by weight, preferably 30 to 45% by weight.
• the weight ratio of graft polymer B) to tetrafluoroethylene polymer E) is between 95: 5 and 60:40.
• the emulsion mixture is then coagulated in a known manner, for example by spray drying, freeze-drying or coagulation by adding inorganic or organic salts, acids, bases or organic, water-miscible solvents, such as alcohols, ketones, preferably at temperatures from 20 to 150 ° C., in particular from 50 to 100 ° C. If necessary, can be dried at 50 to 200 ° C, preferably 70 to 100 ° C.
• Suitable tetrafluoroethylene polymer emulsions are commercially available products and are offered, for example, by DuPont as Teflon® 30 N.
• thermoplastic molding compositions according to the invention can be used for polycarbonates, graft polymers or for the thermoplastic polymers known additives such as stabilizers, pigments, flow agents, mold release agents, fillers and reinforcing materials and / or antistatic agents.
• the filled or reinforced molding compositions can contain up to 60, preferably 5 to 50% by weight, based on the filled or reinforced molding composition, of fillers and / or reinforcing materials.
• Fillers and / or reinforcing materials.
• Glass fibers, carbon fibers, aramid fibers, etc. are suitable as reinforcing materials.
• Preferred reinforcing materials are glass fibers.
• Preferred fillers, which can also have a reinforcing effect, are glass balls, mica, silicates, quartz, talc, titanium dioxide, wollastonite.
• the molding compositions according to the invention consisting of components A), B), D) and E) and optionally C) and / or optionally further known additives such as stabilizers, pigments, flow agents, mold release agents, fillers and reinforcing materials and / or antistatic agents are prepared, by mixing the respective constituents in a known manner and then melt-compounding or melt-extruding at temperatures of 200 to 330 ° C in conventional units such as internal kneaders or single- or twin-screw extruders, or by mixing solutions of the respective components in suitable organic solvents, for example in chlorobenzene, and evaporate the solution mixtures in common evaporation units, for example in evaporation extruders.
• suitable organic solvents for example in chlorobenzene
• the present invention thus also relates to a process for the production of thermoplastic molding compositions consisting of components A), B), D) and E) and, if appropriate, component C), stabilizers, pigments, flow agents, fillers and reinforcing materials, mold release agents and / or antistatic agent, which is characterized in that components A), B), D) and E) and optionally component C), stabilizers, pigments, flow agents, fillers and reinforcing materials, mold release agents and / or antistatic agents after mixing melt-compounded or melt-extruded at temperatures of 200 to 330 ° C. in conventional units, component E) preferably being used in the form of a coagulated mixture with component B).
• the individual constituents can be mixed in a known manner both successively and simultaneously, both at about 20 ° C. (room temperature) and at a higher temperature.
• moldings of the present invention can be used for the production of moldings of any kind.
• moldings can be produced by injection molding.
• moldings that can be produced are: Housing parts of all types, eg. B. for household appliances such as juicers, coffee machines, mixers, for office machines or cover plates for the construction sector and parts for the motor vehicle sector. They are also used in the field of electrical engineering because they have very good electrical properties.
• Another form of processing is the production of shaped bodies by deep drawing from previously produced plates or foils.
• Particle size always means average particle diameter d50, determined by ultracentrifuge measurements according to W. Scholtan et. al., Colloids, et al. Z. Polymer 250 (1972) pp. 782-796.
• the emulsion of the tetrafluoroethylene polymer was mixed with the emulsion of the SAN graft polymer B) and stabilized with 1.8% by weight, based on polymer solids, of phenolic antioxidants.
• the mixture was coagulated with an aqueous solution of MgSO4 (Epsom salt) and acetic acid at pH 4 to 5, filtered and washed until practically free of electrolytes, then freed from the main amount of water by centrifugation and then at 100 ° C dried a powder. This powder can then be compounded with the other components in the units described.
• Components A), B), C), D) and E) were compounded in a ZSK 53 type twin-screw extruder (Werner and Pfleiderer) at a temperature of 240 ° C.
• Moldings were produced on an injection molding machine at 260 ° C.
• the fire behavior of the samples was determined according to UL Subj. 94 V measured in specimen thicknesses of 1.6 mm.
• the UL-94 test is carried out as follows:
• Substance samples are formed into rods measuring 127 x 12.7 x 1.6 mm.
• the rods are mounted vertically so that the underside of the test specimen is 305 mm above a strip of bandaging material.
• Each test stick is ignited individually by means of two successive ignition processes of 10 s duration, the burning properties after each ignition process are observed and the sample is then evaluated.
• a Bunsen burner with a 10 mm (3.8 inch) high blue flame of natural gas with a thermal unit of 3.73 x 104 kJ / m3 (1,000 BUT per cubic foot) is used to ignite the sample.
• the UL-94 VO classification includes the properties of materials described below that have been tested in accordance with the UL-94 regulation.
• the polycarbonate molding compounds in this class do not contain any samples that burn longer than 10 s after each exposure to the test flame; they do not show a total flame time of more than 50 s when exposed twice to each sample set; they do not contain any samples that burn completely up to the retaining clip attached to the top of the sample; they have no samples that ignite the cotton wool underneath the sample by burning drops or particles; they also do not receive any samples that glow more than 30 s after the test flame has been removed.
• UL-94 classifications refer to samples that are less flame retardant and self-extinguishing and that emit flaming drops or particles. This classification is referred to as UL-94 V-1 and V-2.
• N. b. means "failed" and is the classification of samples that have an afterburn time of> 30 s.
• the notched impact strength was determined in accordance with DIN 53 453 / ISO R 179 on bars measuring 50 x 6 x 4 mm, the bars being provided with a V-shaped notch with a notch depth of 2.7 mm.
• the criterion for the stress crack behavior was the decrease in impact strength (determined on bars measuring 50 x 6 x 4 mm according to DIN 53 453 / ISO R 179) after storage in a fuel simulant bath (mixture of 50% by weight toluene and 50% by weight) .-% isooctane) at room temperature, the test specimens being pre-stretched on an arc template.
• a fuel simulant bath mixture of 50% by weight toluene and 50% by weight
• .-% isooctane mixture of 50% by weight toluene and 50% by weight
• the test specimens being pre-stretched on an arc template.
• the more unfavorable values ie the greater the loss of properties
• Example 1 The starting value for test specimens which have not been pre-stretched and not exposed to the test bath is in each case for both examples ng ("not broken").
• the impact strength of the example according to the invention decreases far less than that observed in the comparative example.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Polyesters Or Polycarbonates (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)
• Treatments Of Macromolecular Shaped Articles (AREA)

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• 1988
  • 1988-06-04 DE DE3819081A patent/DE3819081A1/de not_active Withdrawn
• 1989
  • 1989-05-23 US US07/355,957 patent/US5061745A/en not_active Expired - Lifetime
  • 1989-05-23 EP EP89109211A patent/EP0345522B1/fr not_active Revoked
  • 1989-05-23 ES ES89109211T patent/ES2120943T3/es not_active Expired - Lifetime
  • 1989-05-23 DE DE58909840T patent/DE58909840D1/de not_active Expired - Lifetime
  • 1989-05-31 JP JP1136230A patent/JPH0670177B2/ja not_active Expired - Lifetime

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